Complex metal compounds of azo dyestuffs and process for their production



Patented July 27 1937 UNITED STATES COMPLEX METAL COMPOUND-S OF AZODYESTUFFS AND PROCESS FOR THEIR PRODUCTION Guido von Rosenberg,Ludwigshafen-on-the- Rhine, Germany, assignor to General Aniline Works,Inc., New York, N. Y., a corporation of Delaware No Drawing. Originalapplication December 18,

1934, Serial No. 758,139. Divided and this application March 18, 1936,Serial No. 69,532. In Germany December 23, 1933 10 Claims. (Cl. 260-121)The present invention relates to a process of producing complex metalcompounds of azo dyestuffs. This application has been divided out frommy copending application Ser. No. 758,139, filed the 18th of December1934.

I have found that valuable complex metal compounds of azo dyestufis canbe obtained in a very advantageous manner by causing azo dyestufisproduced by coupling one molecular proportion of tetrazotized3,3'-dimethoxy 4,4 diamino-diphenyl with two molecular proportions of anaphthol to react with heavy metal salts of organic high molecularcarboxylic acids, the reaction being effected at elevated temperatures.In some cases only slightly elevated temperatures such as the boilingtemperature of benzene or the friction heat developed by rolling thereaction components on rollers are sufficient while in other casestemperatures between 150 and 200 C. are necessary. Especiallyadvantageous are such metal compounds as have in their moltenphase anoticeable dissolving power for the dyestufis to be treated at elevatedtemperatures. Metal compounds of the said kind are for example thestearates, oleates, linoleates, naphthenates, resinates of a heavy metalsuch as chromium, copper, iron, nickel, cobalt and lead. The reactionmay be carried out by heating a mixture of the said azo dyestufi and acompound yielding metal either as such or after the addition of suitablecompounds depressing the melting point, for example until the metalcompound melts. Suitable additions depressing the melting point are forexample free. acids such as stearic acid. In many cases it may beadvantageous, in order to produce favorable solution conditions, to addto the reaction mixture water-insoluble organic solvents in which boththe compounds yielding metals and the dyestufis are soluble, as forexample hydrocarbons such as benzene, xylenes, any of the isomericcompounds or mixtures thereof and naphthalene, substituted hydrocarbonssuch as trichlorbenzenes for example commercial trichlorbenzeneconsisting mainly of 1,2,4-trichlorbenzene and nitro benzene, esters,etliers, ketones and printers varnishes. Among the complex metalcompounds, obtainable by the present invention, the complex coppercompounds of the said azo dyestuffs are especially valuable. Thus forinstance the dyestufi containing copper and described in the Examples 1and 2 imparts to the materials to be dyed very pure blue shades, incontrast to the corresponding copper compounds obtained in the knownmanner, which only give violet to bluish violet shades.

In many cases it is not necessary to separate the resulting metalcompounds from the reaction mixture; the reaction mixture itself may beused for coloring. For example if a metal stearate be employed for thepreparation of a complex metal compound, the reaction mixture may bedirectly employed for example for coloring candles; by triturating thesaid azo dyestufi with a printing varnish and then reacting with a metallinoleate by heating a printing ink is obtained.

The following examples will further illustrate the nature of thisinvention but the invention is not restricted to these examples. Theparts are by weight.

Example 1 A mixture of 5.6 parts of the azo dyestufi derived from 1molecular proportion of tetrazotized 3,3-dimethoxy-4,4-d.iaminodipheny1and 2 molecular proportions of beta-naphthol, 14 parts of copperstearate and 150 parts of a xylene for example the commercial mixture ofisomeric xylene is heated to boiling for a short time.

After cooling the whole is filtered by suction and the residue is washedwith acetone and dried. A crystalline product is obtained having a clearblue color and a bronze lustre; it may be employed for example as apigment dyestufi for printing varnishes.

Example 2 1 part of the azo dyestuif derived from 1 molecular proportionof tetrazotized 3,3 dimethoxy- 4,4-diaminodiphenyl and 2 molecularproportions of beta-naphthol is triturated with 3.5 parts of printingvarnish with an addition of 2.2 parts of copper linoleate, the mixturethen being heated at about 100 C. until a sample yields a pure blueshade of color when printed.

If the trituration be carried out on the rollers or in another suitabledevice in which a rise in temperature takes place, the reaction occursat once and provided the operation be continued for a sufiiciently longperiod a paste is obtained which can be employed as a blue color forprinting.

If, instead of the azo dyestufi free from metal described in the firstparagraph of this example, the violet copper compound prepared'therefromin the usual manner be employed, a blue copper compound is likewiseobtained. Theviolet cope per-containing dyestuff may also besubsequently treated with chromium linoleate.

. Example .3 f r A mixture of 1 art of the azo dyestuff derived from 1molecular proportion of tetrazotized 3,3-dimethoxy4,4'-diaminodiphenyland 2 molecular proportions of beta-naphthol, 5 parts of chromiumstearate and 40 parts of commercial trichlorbenzene is heated to boilingfor half an hour whereby the color of the solution changes from violetto blue. After cooling, the whole is allowed to stand for some time; thedeposited dyestuff is filtered ofi by suction, washed and dried. A darkpowder is obtained which when triturated with printing varnish yields agreenish blue shade.

A greenish blue product is obtained from the azo dyestuii derived from 1molecular proportion of tetrazotized 3,3-dimethoxy-4,4-diaminodiphenyland 2 molecular proportions of 2,3-hydroxynaphthoic acid anilide bytreatment with chromium stearate.

What I claim is:-

1. The process of producing complex metal compounds of dyestuffs whichcomprises heating in the absence of water an. azo dyestufi produced bycoupling one molecular proportion of tetrazotized3,3'-dimethoxy-4,4-diaminodiphenyl with two molecular proportions of anaphthol, with a heavy metal salt of an organic high-molecularcarboxylic acid selected from the group consisting of naphthenic acids,resinic acids and aliphatic carboxylic acids as contained in naturalfats, oils and waxes.

2. The process of producing complex metal compounds of dyestuffs whichcomprises heating in the absence of water the azo dyestuff produced bycoupling one molecular proportion of tetrazotized3,3-dimethoxy-4,4'-diaminodiphenyl with two molecular proportions ofbeta-naphthol, with a heavy metal salt of an organic high-molecularcarboxylic acid selected from the group consisting of naphthenic acids,resinic acids and aliphatic carboxylic acids as contained in naturalfats, oils and waxes.

3. The process of producing complex metal compounds of dyestuffs whichcomprises heating in the absence of water the azo dyestuff produced bycoupling one molecular proportion of tetrazotized3,3-dimethoxy-4,4-diaminodiphenyl with two molecular proportions of2,3-hydroxynaphthoic acid anilide, with a heavy metal salt of an organichigh-molecular carboxylic acid selected from the group consisting ofnaphthenic acids, resinic acids and aliphatic carboxylic acids ascontained in natural fats, oils and waxes.

4. The process of producing complex metal compounds of dyestuffs whichcomprises heating in the absence of water an azo dyestuff produced bycoupling one molecular proportion of tetrazotized3,3-dimethoxy-4,4-diaminodiphenyl with two molecular proportions of anaphthol, with a heavy metal salt of an organic highmolecular carboxylicacid selected from the group consisting of naphthenic acids, resinicacids and aliphatic carboxylic acids as contained in natural fats, oilsand waxes in the presence of a compound depressing the melting point ofthe said salt.

5. The process of producing complex metal compounds of dyestufis whichcomprises heating in the absence of water an azo dyestufi produced bycoupling one molecular proportion of tetrazotized3,3'-dimethoxy-4,4-diaminodiphenyl with with two molecular proportionsof a naphthol, with a heavy metal salt of an organic highmolecularcarboxylic acid selected from the group consisting of naphthenic acids,resinic acids and aliphatic carboxylic acids as contained in naturalfats, oils and waxes in the presence of a waterinsoluble organicvehicle, in which the dyestuff to be treated and the said salt aresoluble.

6. The process of producing complex metal compounds of dyestuffs whichcomprises triturating in the absence of water in a suitable mechanicaldevice a mixture of an azo dyestufi produced by coupling one molecularproportion of tetrazotized 3,3-dimethoxy-4,4-diaminodiphenyl with twomolecular proportions of a naphthol, with a heavy metal salt of anorganic highmolecular carboxylic acid selected from the group consistingof naphthenic'acids, resinic acids and aliphatic carboxylic acids ascontained in natural fats, oils and waxes and an organic vehicle, inwhich the dyestuff to be treated and the said salt are soluble, thereaction temperature being developed by the friction heat of the movingparts of the mechanical device.

7. The process of producing complex metal compounds of dyestuffs whichcomprises heating in the absence of water an azo dyestuff produced bycoupling one molecular proportion of tetrazotized3,3-dimethoxy-4,4'-diaminodiphenyl with with two molecular proportionsof a naphthol, with a heavy metal salt of an organic highmolecularcarboxylic acid selected from the group consisting of naphthenic acids,resinic acids and aliphatic carboxylic acids as contained in naturalfats, oils and waxes in the presence of a waterinsoluble organicsolvent, in which the dyestuff to be treated and the said salt aresoluble, at the boiling point of the said organic solvent.

8. As a new composition of matter, the reac tion mixture comprisingcomplex metal compounds of dyestuffs produced by heating in the absenceof water an azo dyestufi obtained by coupling one molecular proportionof tetrazotized 3,3'-dimethoxyl-4,4-diaminodiphenyl with two molecularproportions of a naphthol, with a heavy metal salt of an organichigh-molecular carboxylic acid selected from the group consisting ofnaphthenic acids, resinic acids and aliphatic carboxylic acids ascontained in natural fats, oils and waxes.

9. As a new composition of matter, the reaction mixture comprisingcomplex metal compounds of dyestuffs produced by heating in the absenceof water an azo dyestufi produced by coupling one molecular proportionof tetrazotized 3,3- dimethoxy-4A-diaminodiphenyl with two molecularproportions of a naphthol, with a heavy metal salt of an organichigh-molecular carboxylic acid selected from the group consisting ofnaphthenic acids, resinic acids and aliphatic carboxylic acids ascontained in natural fats, oils and waxes in the presence of awater-insoluble organic solvent, in which the dyestuff to be treated andthe said salt are soluble.

10. A complex copper compound giving pure blue shades to the dyedmaterial, produced by heating in the absence of water the dyestuif,derived from one molecular proportion of tetrazotized3,3-dimethoxy-4,4-diaminodiphenyl with two molecular proportions ofbeta-naphthol, with a copper salt of an organic high-molecularcarboxylic acid selected from the group consisting of naphthenic acids,resinic acids and aliphatic h carboxylic acids as contained in naturalfats, oils and waxes.

GUIDO VON ROSENBERG.

